EP0631615B1 - Composition de barre de savon comprenant du silicone - Google Patents

Composition de barre de savon comprenant du silicone Download PDF

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Publication number
EP0631615B1
EP0631615B1 EP94905084A EP94905084A EP0631615B1 EP 0631615 B1 EP0631615 B1 EP 0631615B1 EP 94905084 A EP94905084 A EP 94905084A EP 94905084 A EP94905084 A EP 94905084A EP 0631615 B1 EP0631615 B1 EP 0631615B1
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Prior art keywords
surfactant
silicone
weight
soap
composition according
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EP94905084A
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German (de)
English (en)
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EP0631615A1 (fr
Inventor
Kevin Michael Finucane
Frederick Silvio Osmer
James Joseph Corr
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/126—Acylisethionates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention relates to soap bar compositions in which most or all of the soap has been replaced by other surfactants. Such compositions, in which significant amounts of soap have been removed, are softer, stickier and accordingly more difficult to process into bars.
  • the present invention relates, in particular, to the use of small amounts of silicone or mixtures of silicones of defined viscosity (i.e., centistokes) which allow the detergent bars to be more efficiently processed.
  • soap has been utilized as a skin cleaner. Soap is, however, a very harsh chemical. The use of soap, especially in cold climates, can result in irritated and cracked skin. Benefits which arise from the use of soap include lower cost, ease of manufacture into bars and good lathering properties.
  • the soap pellets (i.e., chips) formed during manufacture i.e., formed after mixing the ingredients, solidifying on a chill roll, and refining to form chips
  • the pellets or chips/noodles will melt on a valve used to transfer the chips to storage in a container/silo. Clogging the machinery such that the chips cannot be readily stored means that the process cannot be stopped and chips cannot be stored until a future time when the chips will be further mixed, refined, extruded, cut and stamped.
  • failure to allow storage means that the first part of the process cannot be run as a batch process (where chips can be stored) and must be run from mixing of ingredients until bar extrusion and stamping.
  • This present invention is directed to those compositions which can be readily processed from chip formation to silo storage thereby allowing an intermediate storage step.
  • compositions are those in which the amount of soap in the composition is very low relative to surfactant, i.e., at level less than 25% by weight of the composition, usually less than 15% by weight.
  • Another way of looking at the problem is to determine when the composition of the pellets is sufficiently tacky that they clog machinery and lower throughput levels (i.e., rate of plodded bars coming out of a plodder) to economically unacceptable rates.
  • silicone in bar compositions comprising silicone is known in the art, for example, from U.S. Patent No. 5,154,849.
  • silicone is used as a skin mildness/moisturizing aid and must be used in amounts sufficient to perceive these effects (e.g. from 0.5% to 20%). Thus, the silicone appears always to be used in amounts of at least several percents by weight and it is not exemplified at less that 5%. There is certainly no recognition of a critical window, not only in amount (i.e., from 0.1 to 0.9% by weight), but also in the viscosity of the silicone, as in the silicone of the present invention.
  • the prior art also requires the presence of at least some silicone gum (claim 1) and this gum must have a molecular weight of at least 200,000 (claim 9).
  • the silicone of the subject invention is used in the absence of gum and is not itself a silicone gum.
  • the tackiness values associated with the replacement of soap by milder surfactants
  • the defined window of silicone lubricates the compositions just enough so that they process more readily without clogging or sticking to machinery.
  • the compositions allow a synthetic soap composition to be noodled by a refiner at a faster rate than the analogous compositions in which silicone is absent.
  • the invention provides a detergent bar composition comprising:-
  • the silicone compound or mixture of silicone compounds (1) provide improved noodle or chip rate production (e.g., serving as a processing aid) after the bar composition is mixed, chill rolled and refined and (2) lower tackiness of the noodles (as measured from bar composition minus final additives such as perfume and colorants)
  • silicone compound or mixture of silicone compounds allows soap chips/noodles formed from the mixing of these compounds to be made in a batch process and stored in a container or silo, if desired, prior to further refining, plodding and stamping. Thus, this allows the process to be decoupled such that noodles can be stored and used on a later occasion, rather than having to utilize the noodles as they are made.
  • Typical mild detergent bar compositions will preferably comprise less than 15% by weight soap, more preferably less than 5% soap and most preferably less than 3% soap.
  • soap is used herein in its popular sense, i.e., the alkali metal or alkanol ammonium salts of aliphatic alkane- or alkene monocarboxylic acids.
  • Sodium, potassium, mono-, di- and tri-ethanol ammonium cations, or combinations thereof, are suitable for purposes of this invention.
  • sodium soaps are preferably used in the compositions of this invention, but from 1% to 25% of the total soap content may be potassium soaps.
  • Preferred soaps are the well known alkali metal salts of natural or synthetic aliphatic (alkanoic or alkanoic) acids having 12 to 22 carbon atoms, preferably 12 to 18 carbon atoms. They may be described as alkali metal carboxylates of acrylic hydrocarbons having 12 to 22 carbon atoms.
  • Soaps having the fatty acid distribution of coconut oil may provide the lower end of the broad molecular weight range.
  • Those soaps having the fatty acid distribution of peanut or rapeseed oil, or their hydrogenated derivatives may provide the upper end of the broad molecular weight range.
  • soaps having the fatty acid distribution of coconut oil or tallow, or mixtures thereof since these are among the more readily available fats.
  • the proportion of fatty acids having at least 12 carbon atoms in coconut oil soap is about 85%. This proportion will be greater when mixtures of coconut oil and fats such as tallow, palm oil, or non-tropical nut oils or fats are used, wherein the principle chain lengths are C 16 and higher.
  • Preferred soap for use in the compositions of this invention has at least about 85% fatty acids having 12-18 carbons atoms.
  • Coconut oil employed for the soap may be substituted in whole or in part by other "high-lauric” oils, that is, oils or fats wherein at least 50% of the total fatty acids are composed of lauric or myristic acids and mixtures thereof.
  • These oils are generally exemplified by the tropical nut oils of the coconut oil class. For instance, they include: palm kernel oil, babassu oil, ouricuri oil, tucum oil, cohune nut oil, murumuru oil, jaboty kernel oil, khakan kernel oil, dika nut oil, and ucuhuba butter.
  • a most preferred soap is a mixture of 15% to 20% coconut oil and 80% to 85% tallow. These mixtures contain about 95% fatty acids having 12 to 18 carbon atoms.
  • the soap may be prepared from coconut oil, in which case the fatty acid content is about 85% of C 12 -C 18 chain length.
  • the soaps may contain unsaturation in accordance with commercially acceptable standards. Excessive unsaturation is normally avoided.
  • Soaps may be made by the classic kettle boiling process or modern continuous soap manufacturing processes wherein natural fats and oils such as tallow or coconut oil or their equivalents are saponified with an alkali metal hydroxide using procedures well known to those skilled in the art.
  • the soaps may be made by neutralizing fatty acids, such as lauric (C 12 ), myristic (C 14 ), palmitic (C 16 ), or stearic (C 18 ) acids with an alkali metal hydroxide or carbonate.
  • the first synthetic surfactant is an anionic detergent active which may be an aliphatic sulfonates, such as a primary alkane (e.g., C 8 -C 22 ) sulfonate, primary alkane (e.g., C 8 -C 22 ) disulfonate, C 8 -C 22 alkene sulfonate, C 8 -C 22 hydroxyalkane sulfonate or alkyl glycerol ether sulfonate (AGS); or aromatic sulfonates such as alkyl benzene sulfonate.
  • a primary alkane e.g., C 8 -C 22
  • primary alkane e.g., C 8 -C 22
  • disulfonate C 8 -C 22 alkene sulfonate
  • C 8 -C 22 hydroxyalkane sulfonate C 8 -C 22 hydroxyalkane sulfonate
  • the first synthetic surfactant may also be an alkyl sulfate (e.g., C 12 -C 18 alkyl sulfate) or alkyl ether sulfate (including alkyl glycerol ether sulfates).
  • alkyl ether sulfates are those having the formula: RO(CH 2 CH 2 O) n SO 3 M wherein R is an alkyl or alkenyl having 8 to 18 carbons, preferably 12 to 18 carbons; n has an average value of greater than 1.0, preferably greater than 3; and M is a solubilizing cation such as sodium, potassium, ammonium or substituted ammonium. Ammonium and sodium lauryl ether sulfates are preferred.
  • the first synthetic surfactant may also be an alkyl sulfosuccinates (including mono-and dialkyl, e.g., C 6 -C 22 sulfosuccinates); alkyl and acyl taurates; alkyl and acyl sarcosinates; sulfoacetates; C 8 -C 22 alkyl phosphates and phosphates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates; C 8 -C 22 monoalkyl succinates and maleates, sulphoacetates, alkyl glucosides and acyl isethionates.
  • alkyl sulfosuccinates including mono-and dialkyl, e.g., C 6 -C 22 sulfosuccinates
  • alkyl and acyl taurates alkyl and acyl sarcosinates
  • Sulfosuccinates may be monoalkyl sulfosuccinates having the formula: R 4 O 2 CCH 2 CH (SO 3 M)CO 2 M; and amide-MEA sulfosuccinates of the formula:- R 4 CONHCH 2 CH 2 O 2 CCH 2 CH (SO 3 M)CO 2 M wherein R 4 ranges from C 8 -C 22 alkyl, preferably C 12 -C 15 alkyl and M is a solubilizing cation such as sodium, potassium, ammonium or triethanolammonium cation.
  • Sarcosinates are generally indicated by the formula:- R 5 CON(CH 3 )CH 2 CO 2 M wherein R 5 ranges from C 8 -C 20 alkyl and M is a solubilizing cation.
  • Taurates are generally identified by formula:- R 2 CONR 3 CH 2 CH 2 SO 3 M wherein R 2 ranges from C 8 -C 20 alkyl, R 3 ranges from C 1 -C 4 alkyl and M is a solubilizing cation such as sodium, postassium, ammonium or triethanolammonium.
  • the first synthetic surfactant are the C 8 -C 18 acyl isethionates. These esters are prepared by reaction between an alkali metal isethionate with mixed aliphatic fatty acids having from 6 to 18 carbon atoms and an iodine value of less than 20. At least 75% of the mixed fatty acids have from 12 to 18 carbon atoms and up to 25% have from 6 to 10 carbon atoms.
  • Acyl isethionates when present, will generally range from 10% to 70% by weight of the total composition. Preferably, this component is present from 30% to 60%.
  • the acyl isethionate may be an alkoxylated isethionate such as is described in Ilardi et al., US-A-5 433 894.
  • This compound has the general formula:- wherein R is an alkyl group having 8 to 18 carbons, m is an integer from 1 to 4, X and Y are hydrogen or an alkyl group having 1 to 4 carbons and M + is a monovalent cation such as, for example, sodium, potassium, ammonium or triethanolammonium cation.
  • the first synthetic surfactant will comprise from about 10 to 70% of the composition, preferably 30-70%, most preferably 40-60% of the composition.
  • the second synthetic surfactant of the invention may be any of the anionic surfactants discussed above except that it should be different from the first synthetic surfactant.
  • the second synthetic surfactant may also be any of the amphoteric or nonionics discussed below as well as a mixture of the anionic, amphoteric and/or nonionic surfactants.
  • Amphoteric detergents which may be used in this invention include at least one acid group. This may be a carboxylic or a sulphonic acid group. They include quaternary nitrogen and therefore are quaternary amido acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms. They will usually have the following structural formula:- where
  • Suitable amphoteric detergents within the above general formula include simple betaines of formula:- and amido betaines of formula: where m is 2 or 3.
  • R 1 , R 2 , and R 3 are as hereinbefore defined for amphoteric detergents.
  • R 1 may, in particular be, a mixture of C 12 and C 14 alkyl groups derived from coconut so that a least half, preferably at least three quarters, of the groups R 1 have 10 to 14 carbon atoms.
  • R 2 and R 3 are preferably methyl.
  • amphoteric detergent is a sulphobetaine of formula:- or where m is 2 or 3, or variants of these in which -(CH 2 ) 3 SO 3 - is replaced by
  • R 1 , R 2 and R 3 are as hereinbefore defined in respect of amido betaines.
  • Particularly preferred anionic second synthetic surfactants are betaines, sulfosuccinates and alkoxylated isethionates.
  • the nonionic which may be used as the second synthetic surfactant of the invention include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C 6 -C 22 ) phenols-ethylene oxide condensates, the condensation products of aliphatic (C 8 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • the nonionic may also be a sugar amide, such as a polysaccharide amide.
  • the surfactant may be one of the lactobionamides described in U.S. Patent No. 5 389 279 to Au et al., or it may be one of the sugar amides described in U.S. Patent No. 5,009,814 to Kelkenberg.
  • the second synthetic surfactant i.e., second anionic nonionic and/or amphoteric compound or mixture
  • the second synthetic surfactant is preferably incorporated into the composition at a level of less than 20% by weight, preferably 1 to 15% by weight of the composition.
  • Free fatty acids of 8-22 carbon atoms may also be desirably incorporated within the compositions of the present invention. Some of these fatty acids are included as superfatting agents and others as skin feel and creaminess enhancers. Superfatting agents enhance lathering properties and may be selected from fatty acids of carbon atoms numbering 8-18, preferably 10-16, in an amount up to 35% by weight of the composition. Skin feel and creaminess enhancers, the most important of which is stearic acid, are also desirably present in these compositions.
  • Skin mildness improvers also preferably used in the composition of the invention are salts of isethionate.
  • Effective salts cations may be selected from the group consisting of alkali metal, alkaline earth metal, ammonium, alkyl ammonium and mono-, di- or tri-alkanolammonium ions.
  • Specifically preferred cations include sodium, potassium, lithium, calcium, magnesium, ammonium, triethylammonium, monoethanolammonium, diethanolammonium or triethanolammonium ions.
  • mildness improver is simple, unsubstituted sodium isethionate of the general formula given hereinbefore wherein R is hydrogen.
  • the skin mildness improver will preferably be present at a level of from 0.5 to 50%, more preferably 1 to 25%, and most preferably 3 to 10%, by weight of the total composition.
  • compositions may be needed with these compositions.
  • the amount of these chemicals and adjuncts may range from 1% to 40% by weight of the total composition.
  • a suds-boosting detergent salt may be incorporated.
  • Illustrative of this type additive are salts selected from the group consisting of alkali metal and organic amine higher aliphatic fatty alcohol sulfates, alkyl aryl sulfonates, and the higher aliphatic fatty acid taurinates.Adjunct materials including germicides, perfumes,colorants, pigments such as titanium dioxide and water may also be present.
  • Silicone compounds useful in the present invention are preferably non-volatile and preferably selected from polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polysiloxanes with amino functional substitutions, or polyether siloxane copolymers. They may be endcapped with any number of moieties, including, for example, methyl, hydroxyl, ethylene oxide, propylene oxide, amino, and carboxyl. Mixtures of these materials may also be used and are preferred in certain executions. Additionally, volatile silicones may be used as part of the silicone mixture so long as the final mixture is non-volatile.
  • the polyalkyl siloxanes that may be used include, for example, polydimethyl siloxanes with viscosities ranging from about 10,000 to about 200,000 m 2 /s (centistokes). These siloxanes are available, for example, from the General Electric Company as the Viscasil® series and from Dow Corning as the Dow Corning 200® series. The viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970. Preferably the viscosity ranges from 10,000 m 2 /s (centistokes) to 150,000 centistokes and most preferably from 10, 000 m 2 /s (centistokes) to 100,000 centistokes.
  • the polyalkylaryl siloxanes that may be used include, for example, polymethylphenylsiloxanes having viscosities of from 12,000 to 200,000 m 2 /s centistokes. These siloxanes are available, for example, from the General Electric Company as SF 1075® methyl phenyl fluid or from Dow Corning as 556® Cosmetic Grade Fluid. Additionally, poly(dimethyl siloxane) (diphenyl siloxane) copolymers having a viscosity in the range of from about 10,000 to about 200,000 m 2 /s (centistokes) are useful.
  • the polyether siloxane copolymer that may be used is, for example, a polypropylene oxide modified dimethylpolysiloxane (e.g., Dow Corning DC-1248 ® , although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
  • a polypropylene oxide modified dimethylpolysiloxane e.g., Dow Corning DC-1248 ® , although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
  • silicone liquids or mixtures of silicone liquids having a viscosity of from 10,000 to 200,000, preferably 40,000 to 150,000 m 2 /s (centistokes) are used.
  • the silicone compound or compounds of the invention may be used as such or in the form of an emulsion composition, for example 50% water and 50% silicone compound.
  • the silicone used in such an emulsion has a viscosity of from 10,000 to 200,000, preferably 10,000 to 150,000 m 2 /s (centistokes).
  • the silicone compound may be used in an amount 0.1 to 0.9% preferably 0.1-0.75%, more preferably 0.1-.0.5% by weight of the composition.
  • the invention provides a process for reducing stickiness and increasing noodle rates of soap noodles passing from a refiner to a silo for storing said noodles prior to subsequent processing which method comprises mixing 10-70% of a first synthetic surfactant which is an anionic surfactant; from 1%-20% of a surfactant selected from a second anionic surfactant (differing from the first), a nonionic surfactant, an amphoteric surfactant and mixtures thereof; 0-25% free fatty acid, 0-35% soap and 0.1-0.9% of a silicone compound or mixture of silicone compounds having a viscosity of from 10,000 to 200,000 m 2 /s (centistokes).
  • the process comprises mixing the various compounds of the composition at a temperature in the range 65.5-149°C (150-300°F) for a time from 15 minutes to about 24 hours depending on desired moisture values.
  • the components of the bar formulations are intimately mixed by mixing the various components in an aqueous slurry, typically using 6 to 15% by weight water (94 to 85% by weight solids) at a temperature in the range 100 to 200°C.
  • the slurry can be drum-dried to a moisture content up to 9% in the dry mix.
  • the components can be mixed dry, preferably in a mechanical mixer such as a Werner-Pfleiderer ® or Day ® mixer.
  • 85°C (185°F) a few hours of mixing may be necessary to dry the mixture to the desired moisture, while at 115°C (240°F) a smooth blend will be obtained in approximately one half hour.
  • the time can be reduced by further increasing the temperature, which will of course be kept below a temperature at which any of the components would degrade.
  • the components can be added together, or it may be desirable to mix the lathering detergent first with water and then incorporate the other ingredients.
  • the composition is cooled and solidified, typically using a chilled flaker (i.e., chill roll), to form small chips. This is often followed by further cooling the chips on a so-called “aging apron", which is essentially a conveyer belt which carries the chips as they come out of the chill roll.
  • chill roll a chilled flaker
  • the chips may either (1) be placed through a refiner wherein mechanical energy is used (e.g., in the form of an airveying valve) to noodle the synthetic soap and then discharge the noodles through an airveying valve into a receptacle/silo or (2) they may be further mixed, sent to a refiner/plodder, cut and stamped.
  • mechanical energy e.g., in the form of an airveying valve
  • the chips follow the first route above, they must be sufficiently hard that they don't melt and clog the machinery (e.g., cause the airveying valve to stop rotating), yet not so hard that they will not later be able to be plodded and stamped.
  • throughput rates of the noodles coming through the refiner are relatively low. While not wishing to be bound by theory, this may be a combination of the fact that the chips/noodles are too soft and clog machinery over time and/or because the silicone is a process aid which mechanically helps in noodle formation. While the noodle rates are not absent altogether, they are low enough as to make the process economically unviable.
  • the use of the silicone compound(s) allows a refiner and storage step to be used (i.e., be economically viable) after chips come off an aging apron (following the chill roll).
  • Figure 1 is a schematic drawing of 7 steps normally taken in preparation of a final bar from mixing to cutting. In the absence of the silicone component; throughput rates at steps 3 and 4 become so low that overall production rates are severely reduced.
  • the extrusion of the final synthetic soap bar was not done at a commercial plant, but at a small pilot plant. All product was accordingly extruded using a Mazzoni M-150 ® refiner/plodder.
  • the screw diameter was 150 mm while the pressure plate opening was 49.5 mm by 27.5 mm.
  • the refiner screw was run at 15.0 RPM.
  • a typical commercial packing line plodder would be a Mazzoni B300/3500 ® which is capable of plodding a pure soap bar composition at a rate of 3500 Kg/hr. (i.e. 9443-10072 kg/s [7500-8000 lbs/hr].).
  • the tackiness of the bars of the invention is measured using a tackiness measurement device as described below.
  • Measurement is accomplished essentially by placing an object of known surface area and impaling this object (using the conical area of the object) into the bar billet.
  • the object is a pointed metal cylinder made of aluminum which penetrates the bar.
  • the object is shaped like a sharpened pencil and comprises both a top cylindrical section and a bottom conical section which conical section initially impales the bar.
  • the overall length of the pointed cylinder was 64 mm with the length of the cylindrical section being 51 mm and the length of the conical section being 13mm. Diameter was 25.5 mm. Surface area of the cone was 729.4 mm 2 . Since the entire conical section is used to impale the soap billet each time, the surface area is kept constant and the force measurements can be compared directly.
  • the cylinder is placed through a centering bushing located on a bridge and is positioned over the soap billet which is held in a vise attachment.
  • the pointed cylinder is then pushed into the soap billet in such a manner that the top of the cylinde is flush with the top of the centering bushing. This ensures that the cylinder is impaled the same distance each time and therefore the surface area is constant.
  • There is a threaded hook inserted into the top of the cylinder. This hook is positioned over an inverted hook protruding from a dynamometer (force measuring device).
  • the dynamometer is attached to a movable arm that is driven by a low RPM motor.
  • the motor is started and the arm begins to move upward away from the soap billet.
  • the moving arm pulls the dynamometer which in turn pulls the cylinder.
  • the dynamometer measures the maximum force applied exactly at the time the cylinder breaks apart from the soap billet.
  • the test is performed three times at each temperature using three different pointed cylinders. The tackiness data is then plotted versus temperature for each bar formulation.
  • compositions tested in the following examples were formulated as follows: Experimental Formula A Component % by Weight Fatty Acid Isethionate 50.00 Free Fatty Acid 25.00 Free Isethionate 5.5 Sulfosuccinate 6.0 Betaine 2.0 Preservatives, dyes, water & other minors Remainder to 100%
  • composition was mixed (with and without silicone compound(s)) and chilled (i.e., on a chill roll) and then further refined.
  • the resulting noodles were then placed directly in a refiner/plodder (e.g., for extrusion) cut and then stamped.
  • a refiner/plodder e.g., for extrusion
  • the reduced tackiness demonstrates that silicone is working as a processing aid and that it can be used to increase noodle production in the first part of the process (thereby allowing the overall total reduction rate to be more economically viable).

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Claims (9)

  1. Composition de pain détergent comprenant :
    (a) de 10 à 70% en poids d'un premier tensioactif synthétique qui est un tensioactif anionique ;
    (b) de 1 à 20% en poids d'un second tensioactif choisi parmi un second tensioactif anionique qui diffère du premier tensioactif synthétique ; un tensioactif non ionique; un tensioactif amphotère et leurs mélanges ;
    (c) 0 à 35% en poids d'acide gras libre ;
    (d) 0 à 25% en poids de savon ; et
    (e) 0,1 à 0,9% en poids d'un composé de silicone ou un mélange de composés de silicone ayant une viscosité de 10.000 à 200.000 m2/s (10.000 à 200.000 centistokes) en l'absence de gomme et qui n'est pas lui-même une gomme de silicone.
  2. Composition selon la revendication 1, dans laquelle le composé (ou les composés) de silicone a une viscosité de 10.000 à 150.000 m2/s (10.000 à 150.000 centistokes).
  3. Composition selon la revendication 1, dans laquelle le premier tensioactif anionique est un acyliséthionate en C8-18.
  4. Composition selon la revendication 1, dans laquelle le second tensioactif est un composé bétaïne.
  5. Composition selon la revendication 1, dans laquelle le second tensioactif est un composé sulfosuccinate.
  6. Composition selon la revendication 1, dans laquelle le second tensioactif comprend un mélange d'un composé bétaïne et d'un composé sulfosuccinate.
  7. Composition selon la revendication 1, dans laquelle le second tensioactif est un iséthionate alcoxylé.
  8. Composition selon la revendication 1, dans laquelle le composé de silicone est un liquide.
  9. Procédé de réduction de l'adhésivité et d'augmentation du débit de nouilles des nouilles de savon passant d'un appareil de raffinage à un silo pour le stockage desdites nouilles avant un traitement consécutif, ce procédé comprenant le mélange de :
    (a) de 10 à 70% en poids d'un premier tensioactif synthétique qui est un tensioactif anionique ;
    (b) de 1 à 20% en poids d'un second tensioactif choisi parmi un second tensioactif anionique qui diffère du premier tensioactif synthétique ; un tensioactif non ionique; un tensioactif amphotère et leurs mélanges ; (c) 0 à 35% en poids d'acide gras libre ;
    (d) 0 à 25% en poids de savon ; et
    (e) 0,1 à 0,9% en poids d'un composé de silicone ou un mélange de composés de silicone ayant une viscosité de 10.000 à 200.000 m2/s (10.000 à 200.000 centistokes) en l'absence de gomme et qui n'est pas lui-même une gomme de silicone.
EP94905084A 1993-01-19 1994-01-17 Composition de barre de savon comprenant du silicone Expired - Lifetime EP0631615B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US571593A 1993-01-19 1993-01-19
US5715 1993-01-19
PCT/EP1994/000120 WO1994017172A1 (fr) 1993-01-19 1994-01-17 Composition de barre de savon comprenant du silicone

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EP0631615A1 EP0631615A1 (fr) 1995-01-04
EP0631615B1 true EP0631615B1 (fr) 1998-09-16

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US (1) US5661120A (fr)
EP (1) EP0631615B1 (fr)
AU (1) AU5884594A (fr)
DE (1) DE69413320T2 (fr)
ES (1) ES2123760T3 (fr)
WO (1) WO1994017172A1 (fr)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5780405A (en) * 1996-03-18 1998-07-14 Lever Brothers Company, Division Of Conopco, Inc. Bar composition comprising copolymer mildness actives
WO1997040131A1 (fr) * 1996-04-24 1997-10-30 Unilever Plc Composition synthetique se presentant sous forme de pain et comprenant des tensioactifs alcoxyles
US5795852A (en) * 1996-04-24 1998-08-18 Lever Brothers Company, Division Of Conopco, Inc. Bar composition comprising nonionic polymeric surfacing as mildness enhancement agents
US5935917A (en) * 1996-06-26 1999-08-10 Lever Brothers Company Bar composition comprising entrapped emollient droplets dispersed therein
BR9602897A (pt) * 1996-06-26 1998-04-28 Unilever Nv Composição de barra de sab o
US6376439B2 (en) 1996-06-26 2002-04-23 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Soap bar composition
US5783536A (en) * 1996-06-26 1998-07-21 Lever Brothers Company, Division Of Conopco, Inc. Bar composition comprising additive for delivering benefit agent
US6121216A (en) * 1996-07-11 2000-09-19 Lever Brothers Company, Division Of Conopco, Inc. Enhanced processing of synthetic bar compositions comprising amphoterics based on minimal levels of fatty acid soap and minimum ratios of saturated to unsaturated soap
US5955409A (en) * 1997-03-21 1999-09-21 Lever Brothers Company Bar compositions comprising adjuvant powders for delivering benefit agent
US5770556A (en) * 1997-03-21 1998-06-23 Lever Brothers Company, Division Of Conopco, Inc. Process for making bar compositions having enhanced deposition of benefit agent comprising use of specific spray dryable adjuvant powders
JP2001514307A (ja) 1997-08-25 2001-09-11 コグニス・ドイチュラント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 脂肪酸ポリグリコールエステルスルフェート含有硬質セッケン
EP1007620A1 (fr) * 1997-08-25 2000-06-14 Cognis Deutschland GmbH Savons a base de detergents synthetiques contenant des sulfates d'ester de polyglycol d'acide gras
US5981465A (en) * 1997-10-28 1999-11-09 General Electric Company Silicone composition for bar soap applications
US6051546A (en) * 1997-10-28 2000-04-18 General Electric Company Silicone composition for bar soap applications
US6080714A (en) * 1997-11-20 2000-06-27 Akzo Nobel Nv Solid composition comprising an amphoteric surfactant, a process for its preparation, and the use thereof
US5981451A (en) * 1998-09-23 1999-11-09 Lever Brothers Company Non-molten-mix process for making bar comprising acyl isethionate based solids, soap and optional filler
US6214780B1 (en) * 2000-03-08 2001-04-10 Lever Brothers Company, Division Of Conopco, Inc. Enhanced processing of synthetic bar compositions comprising amphoterics based on minimal levels of fatty acid soap and minimum ratios of saturated to unsaturated soap
US6789290B2 (en) 2001-07-02 2004-09-14 Rug Doctor, L.P. Dual mode carpet cleaning device
MXPA05008199A (es) * 2003-01-29 2005-09-30 Unilever Nv Composicion de detergente.
DE10318325A1 (de) * 2003-04-19 2004-10-28 Beiersdorf Ag Festes Reinigungsstück, enthaltend elastomere Polymere
US6849585B1 (en) 2004-01-13 2005-02-01 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Bar with good user properties comprising acid-soap complex as structurant and low levels of synthetic
EP2747841A2 (fr) * 2011-08-25 2014-07-02 Unilever N.V. Composition
IT201900003951A1 (it) * 2019-03-19 2020-09-19 Desmet Ballestra S P A Impianto per la realizzazione di un prodotto, in particolare costituito da un prodotto tensioattivo

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1381773A (en) * 1972-05-31 1975-01-29 Unilever Ltd Detergent bar
US4673525A (en) * 1985-05-13 1987-06-16 The Procter & Gamble Company Ultra mild skin cleansing composition
US4976953A (en) * 1987-03-06 1990-12-11 The Procter & Gamble Company Skin conditioning/cleansing compositions containing propoxylated glycerol derivatives
US4919838A (en) * 1988-09-30 1990-04-24 Hubert M. Tibbetts Bar shampoo and skin soap
GB8912391D0 (en) * 1989-05-30 1989-07-12 Unilever Plc Shampoo composition
US5011681A (en) * 1989-10-11 1991-04-30 Richardson-Vicks, Inc. Facial cleansing compositions
US5085857A (en) * 1989-12-04 1992-02-04 Chesebrough-Pond's Usa Co. Conditioning shampoo comprising a surfactant, a non-volatile silicone oil and guar hydroxypropyltrimonium chloride as a cationic conditioning polymer
US5154849A (en) * 1990-11-16 1992-10-13 The Procter & Gamble Company Mild skin cleansing toilet bar with silicone skin mildness/moisturizing aid
JPH06506260A (ja) * 1991-03-21 1994-07-14 ザ、プロクター、エンド、ギャンブル、カンパニー 改善された加工性を有する温和な化粧用洗浄固形石鹸
JPH07501077A (ja) * 1991-11-22 1995-02-02 リチャードソン、ビックス、インコーポレーテッド 組合せパーソナルクレンジング及びモイスチャライジング組成物
ES2094309T3 (es) * 1991-11-25 1997-01-16 Unilever Nv Esteres de acidos grasos de acido isetionico alcoxilado y composiciones detergentes que comprenden los mismos.
US5308526A (en) * 1992-07-07 1994-05-03 The Procter & Gamble Company Liquid personal cleanser with moisturizer

Also Published As

Publication number Publication date
WO1994017172A1 (fr) 1994-08-04
EP0631615A1 (fr) 1995-01-04
US5661120A (en) 1997-08-26
DE69413320T2 (de) 1999-02-25
ES2123760T3 (es) 1999-01-16
DE69413320D1 (de) 1998-10-22
AU5884594A (en) 1994-08-15

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